JPH0778091B2 - Photopolymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial field of application" The present invention relates to a photopolymerizable composition containing a novel photopolymerizable initiator. More specifically, lithographic printing, resin convex plate, resist or photomask for making a printed circuit board,
The present invention relates to a high-sensitivity and spectrally sensitized photopolymerizable composition that can be used for producing a black-and-white or color transfer coloring sheet or a coloring sheet.

"Prior Art" A photopolymerizable composition is basically a photopolymerization initiator and an addition-polymerizable compound containing two or more ethylenically unsaturated bonds in the molecule (hereinafter referred to as "multifunctional monomer"). Including,
When it is irradiated with light, it cures, its adhesiveness changes, and it becomes insoluble in solvents. Utilizing these properties, it is widely used in photography, printing, metal surface processing, ink and the like. Concepts and application examples are described in many books. For example,
"Light Sensitive Systems" by Coser, Jay Willie and Sons New York
"Light Sensitive Systems" J. Wiley & Sons, New Yo
rk) pp. 158-193, 1965, and K. J. Jacobson.
"Imaging Systems" by R. Y. Jacobson JAE Wheelie and Sands New York ("Imaging Syste" by KI Jacobson, RE Jacobson)
ms ”J. Wiley & Sons, New York) pp. 181-222, 1976.

Further, in recent years, as an image forming method using a photopolymerizable composition, an image forming system using a photosensitive microcapsule in which a photopolymerizable composition is encapsulated in a microcapsule has been proposed. For example, JP-A-57-124343 and JP-A-57-179836
JP-A-57-197538 discloses that a color-forming sheet coated with a microcapsule containing a photopolymerizable composition comprising a vinyl compound and a photopolymerization initiator and a dye is superposed on the image-receiving sheet after exposure and a pressure is applied to the whole. A method of forming a dye image thereby is disclosed.

In recent years, attempts have been made to spectrally sensitize these photopolymerizable compositions into the visible light region to form a digital image using a laser as a light source, and application to a full-color photosensitive material.

For example, the Journal of the Photographic Society of Japan, Vol. 49, No. 3, 230 (1986) and Functional Materials, September 1983, pages 48-60, describes spectral sensitization of photopolymerizable compositions for use in laser recording. There is.
Further, JP-A-59-189340 describes a method of spectrally sensitizing an organic peroxide initiator with an organic dye. Further, European Patent No. 223,587A1 discloses an organic boron anion salt of an organic cationic dye as a novel photopolymerization initiator.

In particular, the method of using the organic boron compound anion salt of the organic cationic dye compound as a photosensitive initiator has a wide selection range of the cationic dye compound, and can design a photopolymerization initiator composition sensitive to any wavelength. Is a useful method.

"Problems to be Solved by the Invention" However, although these methods can provide a photopolymerization initiator composition sensitive to visible light, satisfactory photosensitivity has not been obtained.

"Object of the Invention" One of the objects of the present invention is to provide a novel photopolymerization initiator composition having high sensitivity and photosensitivity to a light source of visible light or higher. More specifically, a highly sensitive and light source using an organic boron compound anion salt of a novel organic cationic dye, for example, a lithographic printing plate having a photosensitivity to a laser light source, a resin relief printing plate, a resist for forming a printed board or It is intended to provide a photopolymerization initiator composition which can be advantageously used for a photomask. Another object is to provide a photopolymerization initiator composition for microcapsules which can be advantageously used for black-and-white or color image formation and which has high sensitivity and is sensitive to a light source of visible light or higher.

“Means for Solving the Problem” As a result of earnest research, the present inventors have (a) a polymerizable compound having an ethylenically unsaturated bond in the molecule, and (b) an organic cation represented by the following general formula (I). It was discovered that the above object can be achieved by using a photopolymerizable compound represented by the following general formula (II) as the organic cationic dye compound containing an organic boron anion salt compound as a sex dye.

General formula (I) Here, D ⁺ is a cationic dye represented by the general formula (II); R ¹ , R ² , R ³ and R ⁴ may be the same or different, and an alkyl group, a substituted alkyl group, an aryl group, Substituted aryl group, aralkyl group, substituted aralkyl group, alkaryl group, substituted alkaryl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, alicyclic group, heterocyclic group, substituted heterocyclic group A group; R ¹ , R ² , R ³ , and R ⁴ may be a cyclic structure to which two or more groups are bonded.

General formula (II) In the formula, R ¹¹ and R ¹² each represent an alkyl group,
L ¹ , L ² and L ³ represent a methine group. n represents an integer of 0 to 4, and A ¹ , A ² , A ³ , A ⁴ , B ¹ , B ² , B ³ and B ⁴ each represent a hydrogen atom or an electron-withdrawing group (hamet σ> 0). However, at ^{least one} of A ¹ , A ² , A ³ , A ⁴ , B ¹ , B ² , B ³ , and B ⁴ represents an electron-absorbing group.

Examples of the alkyl group represented by R ¹¹ and R ¹² include an alkyl group having 1 to 18 carbon atoms (an unsubstituted alkyl group (for example,
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups such as aralkyl groups (eg benzyl, 2-phenylethyl), hydroxyalkyl groups (eg 2-hydroxyethyl, 3- Hydroxypropyl), carboxyalkyl group (eg, 2-carboxyethyl, 37-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (eg, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl) , A sulfoalkyl group (eg, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-
Sulfobutyl, 2- [3-sulfopropoxy] ethyl,
2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl groups (eg, 3-sulfatopropyl, 4-furatoatobutyl), heterocyclic-substituted alkyl groups (eg, 2- (pyrrolidine-2). -On-1-yl) ethyl, tetrahydrofurfuryl), 2-acetoxyethyl, carbomethoxymethyl,
2-methanesulfonylaminoethyl, allyl group}.

The methine group represented by L ¹ , L ² and L ³ may be substituted, and examples of the substituent include an alkyl group (eg methyl, ethyl), an aryl group (eg phenyl), an aralkyl group (eg benzyl group). ) Or a halogen atom (eg, chlorine atom, bromine atom), a chalcoxy group (eg, methoxy, ethoxy) and the like, and the substituents of the methine chain may form a 4- to 6-membered ring.

R ¹¹ or R ¹² may form a 4- or 6-membered ring together with L ¹ , L ² or L ³ .

Examples of the electron-withdrawing group represented by A ¹ , A ² , A ³ , A ⁴ , A ¹ , B ¹ , B ² , B ³ , B ⁴ include halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), nitro Group, a carbamoyl group (for example, a carbamoyl group, an N-ethylcarbamoyl group,
N-propylcarbamoyl group, N-hexylcarbamoyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, 2-ethylhexyloxycarbonyl group, octyloxycarbonyl group),
Examples thereof include a sulfamoyl group (for example, a sulfamoyl group, an N-butylsulfamoyl group) and a cyano group.

Examples of the organic boron compound anion in the general formula (I) include U.S. Pat. Nos. 3,567,453, 4,307,182 and 4,343,891.
4,447,521, 4,450,227, JP-A-62-150242,
Various compounds can be used with reference to JP-A-62-143044 and the like, but the most preferable compound is R ₁ ═R ₂ ═R ₃ : phenyl, p
- methoxyphenyl, p- Butokishifueniru, p- dimethylamino-phenylalanine or p- chloro R _4: methyl, ethyl, propyl, butyl, compound of n- hexyl or n- heptyl.

As the compound of the general formula (I), an organic boron compound anion salt of an organic cationic dye synthesized with reference to the above-mentioned patents and the like can be used, but any organic cationic dye in the photopolymerizable composition can be used. A salt such as a chloro salt or an iodo salt and any salt of an organic boron compound such as a tetrabutylammonium salt may be added respectively.

Specific examples of the organic boron compound anion salt of the organic cationic dye compound are given below. However, the effects of the present invention are not limited to the following compounds.

The polymerizable compound having an ethylenically unsaturated bond in the composition of the present invention means at least 1 in its chemical structure.
A compound having one ethylenically unsaturated bond and having a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and a mixture of other oligomers and a copolymer thereof. . Examples thereof include unsaturated carboxylic acids and salts thereof, esters with aliphatic polyhydric alcohol compounds, and amides with aliphatic polyhydric amine compounds.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid,
Maleic acid etc.

Examples of the salts of unsaturated carboxylic acids include sodium salts and potassium salts of the aforementioned acids.

Specific examples of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid ester, ethylene glycol diacrylate, triethylene glycol triacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, Propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol Diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraac Rate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, polyester acrylate oligomer.
Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ketylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, pentaerythritol dimethacrylate, penta Erythritol trimethacrylate, dipentaerythritol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis- [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis (p
-(Acryloxyethoxy) phenyl] dimethylmethane and the like. As itaconic acid esters, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-
Examples include butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate. Examples of crotonic acid esters include ethiene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Further, a mixture of the above-mentioned esters can also be mentioned.

Specific examples of amides of an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis-methacrylamide, Examples include diethylenetriamine tris acrylamide, xylylene bis acrylamide, and xylylene bis methacrylamide.

As another example, vinyl containing a hydroxyl group represented by the following general formula (III) in a polyisocyanate compound having two or more kinds of isocyanate groups in one molecule described in JP-B-48-41708. Examples thereof include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a monomer is added.

CH ₂ ═C (R ²¹ ) COOCH ₂ CH (R ²² ) OH (III) (wherein R ²¹ and R ²² represent H or CH ₃ ). Further, a polymer compound having a vinyl group or a vinylidene group, for example, A condensate of a polymer compound having a hydroxyl group, an amino group, an epoxy group, a halogen atom, or a sulfonyloxy group in its side chain with acrylic acid, methacrylic acid, or a derivative thereof can be used in the present invention.

Further, a compound containing a vinyl group in the molecule of a color image forming substance such as a dye or a leuco dye can be used as the polymerizable compound.

The organic boron compound as the organic cationic dye compound is preferably added in the range of 0.01 to 50% by weight with respect to the polymerizable compound.

A novel photopolymerizable composition containing a polymerizable compound having an ethylenically unsaturated bond and a compound having an organic boron compound anion salt of an organic cationic dye compound as exemplified above is used for various applications. You can

For example, a layer containing the photopolymerizable composition and a binder polymer may be provided on a support to obtain the layers of US Pat. Nos. 4,604,342 and 4,4,5.
87,199, 4,629,680, 4,415,652, 4,
No. 431,723, No. 4,550,073, Japanese Published Patent 61-285,444,
With reference to JP-A 61-213213 and the like, for a resist material for making a printing plate or a printed circuit board, Japanese Published Patent No. 62-67529,
With reference to US Pat. No. 4,604,340, etc., color proof materials, etc. can be applied to many fields according to methods known in the art.

Further, since the photopolymerizable composition of the present invention has high sensitivity and is sensitive to visible light, it can be particularly advantageously used for an image forming system utilizing microcapsules.

To use in an image forming system using microcapsules, see, for example, JP-A Nos. 57-197538, 61-130945, and 61-130945.
Reference can be made to 58-88739, 58-88740, and European Patent No. 223,587A1. This image forming method is, for example, coating a microcapsule containing a photopolymerization initiator composition comprising an ethylenic vinyl compound and a photopolymerization initiator and a dye precursor on a support, and exposing the photosensitive sheet imagewise for exposure. Part of the microcapsules are cured, and then a developer sheet is overlaid and pressure is applied to the entire surface to destroy the unexposed parts of the microcapsules, and the color image forming substance (eg, dye precursor) is transferred to the image receiving element (eg, developer). Layer),
This is a method of developing color. The present invention will be described below by taking an image forming system using the microcapsules as an example.

Various additives can be added to the photopolymerizable composition of the present invention depending on the purpose. For example, a thermal polymerization inhibitor, a polymerization accelerator, a color image forming substance (a dye or a dye precursor or a pigment) and the like can be added.

The method for producing a photosensitive material using the photopolymerizable composition of the present invention will be described below.

Although various methods can be used as a method for producing a light-sensitive material, a general production method is to prepare a coating solution by dissolving, emulsifying or dispersing the components of the photosensitive layer in an appropriate solvent, and applying the solution. It comprises a step of obtaining a light-sensitive material by applying the liquid to the support as described above and drying.

Generally, each coating solution is prepared by preparing a liquid composition containing each component for each component, and then mixing each liquid composition. The liquid composition may be prepared for each component, or may be prepared to contain a plurality of components. A part of the components of the photosensitive layer may be added and used at the stage of preparing the liquid composition or the coating solution or after the preparation. Furthermore, as described below, an oily (or aqueous) composition containing one or more components is
Further, a method of preparing a secondary composition by emulsifying in an aqueous (or oily) solvent can also be used.

The polymerizable compound of the photopolymerizable composition of the present invention can be emulsified and contained as droplets in the photosensitive layer, or the periphery of the droplets can be covered with a microcapsule wall. At this time, it is preferable that the organic boron compound anion salt of the organic cationic dye compound is also contained in the droplet.

A thermal polymerization inhibitor may be added to the composition of the present invention mainly for the purpose of preventing polymerization of the photopolymerizable composition during storage. Specific examples of the thermal polymerization inhibitor include, for example, p-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, cuprous chloride, chloranil, naphthylamine, β-naphthol, 2,6-diphenol. Examples thereof include -t-butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, p-toluidine, methylene blue-organic copper and methyl salicylate. These thermal polymerization inhibitors are preferably contained in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated compound.

The composition of the present invention may further use, as a polymerization accelerator, a reducing agent such as an oxygen scavenger and a compound acting as a chain transfer agent of an active hydrogen donor.
Oxygen scavengers that have been found to be useful are phosphines, phosphonates, phosphites, stannous salts and other compounds that are readily oxidized by oxygen. Useful chain transfer agents are N-phenylglycine, trimethylbarbituric acid, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, N, N dimethyl-2,6-diisopropylaniline, N, N-2,4,6. -Pentamethylaniline and other compounds with hydrogen which can be easily extracted by radicals.

The composition of the present invention may contain a dye image-forming substance to remove the unpolymerized portion, and then the polymerized portion may be colored, or the unpolymerized portion may be transferred to an image receiving element to form a color image.

There are various color image-forming substances that can be used in the present invention. For example, dyes and pigments can be cited as those that are themselves colored. When these are used, a color image can be formed by destroying a portion (microcapsule) in which a high molecular polymer is not formed and transferring it to an image receiving material by a suitable method. Dyes and pigments are commercially available as well as publicly known in various documents (eg, "Handbook of Dyes" edited by The Society of Organic Synthesis and Ratioology, published in 1970, "Handbook of Latest Pigments" edited by Japan Pigment Technology Association, published in 1972). Stuff available. These dyes or pigments are used after being dissolved or dispersed.

On the other hand, as an uncolored color image-forming substance, it is colorless or light-colored by itself, but it is colored by some energy such as heating, pressurization, or light irradiation, and itself does not develop color even when energy is applied, Classified as those that develop color when contacted with another component. Known examples of the former are thermochromic compounds, piezochromic compounds, photochromic compounds, and leuco bodies such as triarylmethane dyes, quinone dyes, isodigoide dyes, and azine dyes. These are all heating, pressurization,
It is colored by light irradiation or air oxidation.

Examples of the latter include various systems that develop color by an acid-base reaction between two or more components, a redox reaction, a coupling reaction, a chelate formation reaction, and the like. For example, a color-developing system consisting of a color-forming agent having a partial structure such as lactone, lactam, and spiropyran used for pressure-sensitive paper and an acidic substance (developing agent) such as acid clay or phenols; aromatic diazonium salt or diazotate, System utilizing azo coupling reaction of diazo sulfonates with naphthols, anilines, active methylenes; reaction of hexamethylenetetramine with ferric ion and gallic acid, phenolphthalein-complexonic acid with alkaline earth A chelate-forming reaction such as a reaction with a metal ion; a redox reaction such as a reaction between ferric stearate and pyrogallol or a reaction between silver behenate and 4-methoxy-1-naphthol can be used.

Further, as another example of a system in which the color is developed by the reaction between the two components, it is known that this reaction proceeds by heating. In this case, it is necessary to heat at the same time as the two components are mixed by the microcapsule destruction at the time of pressurization or immediately after pressurization.

As the color former in the color former / developer developer system,
There are (1) triarylmethane compounds, (2) diphenylmethane compounds, (3) xanthene compounds, (4) thiazine compounds, (5) spiropyran compounds, and the like, and specific examples include:
Examples thereof include those described in JP-A-55-27253. Among these, (1) triarylmethane-based and (3) xanthene-based color formers are preferable because many of them have less fog and give high color density. Specific examples include crystal bio-leptlactone, 3-diethylamino-6-chloro-
7- (β-ethoxyethylamino) fluorane, 3-diethylamino-6-methyl-7-anilinofluorane,
3-triethylamino-6-methyl-7-anilinofluorane, 3-cyclohexylmethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-7-
There are o-chloroanilinofluorane and the like, and these may be used alone or in combination.

As the color developer, a phenol compound, an organic acid or a metal salt thereof, an oxybenzoic acid ester, acid clay, etc. are used.

Examples of phenol compounds are 4,4'-isopropylidene-diphenol (bisphenol A), p-tert-
Butylphenol, 2,4-dinitrophenol, 3,4-dichlorophenol, 4,4'-methylene-bis (2,6-di-
tert-butylphenol), p-phenylphenol,
1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 ′ -Methienbis (4-tert-butylphenol), 2,2'-methylenebis (α-phenyl-p-cresol) thiodiphenol, 4,4'-thiobis (6-t
(ert-butyl-m-cresol), sulfonyldiphenol, p-tert-butylphenol-formalin condensate, p-phenylphenol-formalin condensate and the like.

Examples of the organic acid or its metal salt include phthalic acid, phthalic anhydride, maleic acid, benzoic acid, gallic acid, o-toluic acid, p-toluic acid, salicylic acid, 3-tert-butylsalicylic acid and 3,5-di- tert-butylsalicylic acid, 5-
α-methylbenzyl salicylic acid, 3,5- (α-methylbenzyl) salicylic acid, 3-tert-octylsalicylic acid and its zinc, lead, aluminum salt, magnesium salt,
Nickel salt and the like are useful. In particular, the salicylic acid derivative and its zinc salt or aluminum salt are excellent in terms of color developing ability, fastness of a color image, storability of a recording sheet and the like.

Examples of the oxybenzoic acid ester include ethyl p-oxybenzoate, butyl p-oxybenzoate, heptyl p-oxybenzoate, benzyl p-oxybenzoate and the like.

In addition, an oil-absorbing white pigment may be used in combination to diffuse and immobilize the capsule inclusion.

These developers are added as a eutectic with a low-melting heat-fusible substance, or a low-melting compound is added to the surface of the developer particles in order to cause a color reaction by melting at a desired temperature. It is preferable to add it in a fused state.

Specific examples of the low-melting point compound include higher fatty acid amides such as stearic acid amide, erucic acid amide, palmitic acid amide, waxes such as ethylene bisstearamide or higher fatty acid ester, or benzoic acid phenyl derivative, aromatic ether derivative, Alternatively, there is a urea derivative, but it is not limited thereto.

Other color-developing / developing color-developing agents include, for example, phenolphthalein, fluorescein, 2 ', 4', 5 ', 7'-
Tetrabromo-3,4,5,6-tetrachlorofluorescein, tetrabromophenol blue, 4,5,6,7-tetrabromophenolphthalein, eosin, aurincresol red, 2-naphtholphenolphthalein, etc. is there.

As the developer, inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines, triazoles. And nitrogen-containing compounds such as morpholines, piperidines, amidines, formazines and pyridines. Specific examples of these include ammonium acetate, tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine, allylurea, thiourea, methylthiourea,
Allylthiourea, ethylenethiourea, 2-benzylimidazole, 4-phenylimidazole, 2-phenyl-
4-methyl-imidazole, 2-undecyl-imidazoline, 2,4,5-trifuryl-2-imidazoline, 1,2-diphenyl-4,4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1, 2,3-triphenylguanidine, 1,2-ditolylguanidine, 1,2-dicyclohexylguanidine, 1,2-dicyclohexyl-3-phenylguanidine, 1,2,3-tricyclohexylguanidine, guanidine trichloroacetic acid salt, N, N'-dibenzylpiperazine, 4,4'-dithiomorpholine, morpholinium trichloroacetate, 2-amine-benzothiazole,
There is 2-benzoylhydrazino-benzothiazole.

The color image-forming substance of the present invention is used in a proportion of 0.5 to 20 parts by weight, particularly preferably 2 to 7 parts by weight, based on 100 parts by weight of the polymerizable compound. About 1 part by weight of color developer
It is used in a proportion of 0.3 to 80 parts by weight.

When the photopolymerizable composition of the present invention is microencapsulated, it can be prepared by a method known in the art. For example, U.S. Pat.Nos. 2800457 and 2800458, a method utilizing coacervation of a hydrophilic wall-forming material as seen in U.S. Pat.No. 3,287,154, British Patent 990443, Japanese Patent Publication No. 38-19574,
Interfacial polymerization methods such as those found in U.S. Pat. Nos. 42,446,42-771, methods by polymer precipitation as seen in U.S. Pat.Nos. 3,418,250 and 3,660,304, isocyanate-polyol walls as seen in U.S. Pat. Urea-formaldehyde-based or urea-formaldehyde-resorcinol-based wall-forming material found in U.S. Pat.Nos. 4,001,140,4087376,4089802. Method, method using wall forming material such as melamine-formaldehyde resin and hydroxypropyl cellulose found in U.S. Pat. No. 4,025,455, JP-B-36-9168, JP-A-51-9079
In situ due to polymerization of monomers
u) method, electrolytic dispersion cooling method found in British Patent Nos. 952807 and 965074, and spray drying method found in U.S. Patent No. 3111407 and British Patent No. 930422. Although not limited thereto, it is preferable to form a polymer film as a microcapsule wall after emulsifying the core substance.

As a method of producing the microcapsule wall of the present invention, the effect is particularly large when the microencapsulation method by polymerizing the reactant from the inside of the oil droplet is used. That is, it is possible to obtain capsules having a uniform particle size within a short period of time, which are preferable as a recording material having excellent raw storability.

For example, when polyurethane is used as a capsule wall material, a polyvalent isocyanate and a second substance that reacts with it to form a capsule wall (eg, polyol, polyamine)
Is mixed with an oily liquid to be encapsulated, emulsified and dispersed in water, and then the temperature is raised to cause a polymer forming reaction at the oil droplet interface to form a microcapsule wall. At this time, an auxiliary solution having a low boiling point and a strong dissolving power can be used in the oily liquid.

In this case, regarding the polyisocyanate used and the partner polyol and polyamine which react with it, US Pat. Nos. 3,281,383, 3,773,695, 3,793,268 and JP-B-48-40 are used.
347, 49-24159, JP-A-48-80191, 48-84086
, And they can also be used.

As the polyvalent isocyanate, for example, m-phenylene diisocyanate, p-phenylene diisocyanate,
2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl-diisocyanate, 3 ,
3'-Dimethylphenylmethane-4,4'-diisocyanate, xylylene-1,4-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene Diisocyanates such as -1,2-diisocyanate, cyclohexylene-1,2-diisocyanate and cyclohexylene-1,4-diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, toluene-2,4,6- Triisocyanates such as triisocyanate, tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, 2,4-triisocyanate. Diisocyanate and trimethylol Adducts of propane, the adduct of xylylene diisocyanate and trimethylolpropane, there are isocyanate prepolymers such as tolylene diisocyanate and hexane triol adducts.

Examples of polyols include aliphatic and aromatic polyhydric alcohols, hydroxypolyesters, and hydroxypolyalkylene ethers.

The following polyols described in JP-A-60-49991 are also used, ethylene glycol, 1,3-propanediol,
1,4-butanediol, 1,5-pentanediol, 1,6-
Hexanediol, 1,7-heptanediol, 1,8-octanediol, propylene glycol, 2,3-dihydroxybutane, 1,2-dihydroxybutane, 1,3-dihydroxybutane, 2,2-dimethyl-1,3 -Propanediol,
2,4-pentanediol, 2,5-hexanediol, 3-
Methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, dihydroxycyclohexane, diethylene glycol, 1,2,6-trihydroxyhexane, 2-
Phenyl propylene glycol, 1,1,1-trimethylolpropane, hexanetriol, pentaerythritol, pentaerythritol ethylene oxide adduct,
Glycerin ethylene oxide adduct, glycerin, 1,
Condensation products of aromatic polyhydric alcohols such as 4-di (2-hydroxyethoxy) benzene and resorcinol dihydroxyethyl ether with alkylene oxides, p-xylylene glycol, m-xylylene glycol, α,
α'-dihydroxy-p-diisopropylbenzene, 4,
4'-dihydroxy-diphenylmethane, 2- (p, p'-
Dihydroxydiphenylmethyl) benzyl alcohol,
Examples thereof include an adduct of ethylene oxide with bisphenol A and an adduct of propylene oxide with biphenol A. The polyol is preferably used in such a manner that the ratio of the hydroxyl group is 0.02 to 2 mol with respect to 1 mol of the isocyanate group.

Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine and 2-hydroxytriamine. Methylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine,
Examples thereof include amine adducts of epoxy compounds. Polyisocyanates can also react with water to form polymeric substances.

When making the microcapsules, a water-soluble polymer can be used, and the water-soluble polymer may be any of a water-soluble anionic polymer, nonionic polymer and amphoteric polymer.
As the anionic polymer, a natural one or a synthetic one can be used, and examples thereof include those having a —COO ⁻ , ▲ -SO ^- ₃ ▼ group and the like. Specific examples of the anionic natural polymer include arabic gum, alginic acid and pectin, and semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose and lignin sulfonic acid.

Further, synthetic products include maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers and copolymers, Examples include carboxy-modified polyvinyl alcohol.

Examples of the nonionic polymer include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose and the like.

Examples of amphoteric compounds include gelatin.

These water-soluble polymers are used as 0.01-10 wt% aqueous solutions. The particle size of the microcapsules is adjusted to 20 μm or less.

The size of the capsule used in the present invention is 80 μm or less, and particularly preferably 20 μm or less from the viewpoint of storage stability and handleability. If the capsule is too small, it may be erased in the pores of the substrate or in the fiber, but this cannot be generally stated because it depends on the properties of the substrate or support, but 0.1 μm or more is preferable.

The capsule used in the present invention does not substantially change at a pressure of about 10 kg / cm ² or less, and it is preferable that the capsule be broken when a pressure larger than this is applied, but the magnitude of this breaking pressure depends on the application. It is possible to change it, and it is not limited to a specific value, but about 500 Kg / cm
It is preferable to break at a pressure of about ² or less. Depending on the particle size of the capsule, the thickness of the capsule wall, and the type of wall material used,
These pressure characteristics can be controlled.

A solvent may be used together when the polymerizable compound and the color image-forming substance according to the present invention are encapsulated. A solvent can also be used when introducing a reducing agent, a color developing agent, and the like into necessary elements. For example, a solution dissolved in water or a hydrophilic organic solvent can be directly coated on a support together with a binder if necessary, and introduced into a necessary element by a known method such as the method described in U.S. Pat. can do. By using a solvent together with the microcapsules, it is possible to control the degree of destruction of the capsules upon pressurization and the amount of transfer of the color image forming substance in the capsules to the image receiving element. The amount of the solvent used together in the capsule is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the polymerizable compound.

A natural oil or a synthetic oil can be used in combination as the solvent used in the present invention. Examples of these solvents are, for example, cottonseed oil, kerosene, aliphatic ketones, aliphatic esters, paraffins, naphthenic oils, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, alkylated naphthalene, and 1-phenyl-1-xylylethane, 1
-Phenyl-1-p-ethylphenylmethane, 1,1'-
Diarylethanes such as ditolylethane.

Phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate),
Citric acid ester (eg, acetyl citrate tributyl), benzoic acid ester (benzoic acid ester), alkylamide (eg, diethyllaurylamide), fatty acid ester (eg, dibutoxyethyl succinate, dioctyl acerate), trimesic acid ester ( Lower alkyl acetates such as tributyl trimesate), ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate,
Cyclohexanone etc.

The image-receiving element for use with the light-sensitive element using the composition of the present invention is an element for developing and / or fixing the color image-forming substance released from the light-sensitive microcapsules. The light-sensitive microcapsules and the image-receiving element may be in the same layer on the same support, may be in different layers on the same support, and have a layer containing the light-sensitive microcapsules on the support. It may be provided on different supports such as a combination of a light-sensitive sheet and an image-receiving sheet having a layer containing an image-receiving element on the support.

Further, the image-receiving element of the present invention may contain a mordant such as an anionic polymer or a cationic polymer, or may contain both the anionic polymer and the cationic polymer, if necessary.

The binder used in the light-sensitive material and the image-receiving material of the present invention can be contained alone or in combination. As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical, for example, gelatin, gelatin derivatives, proteins such as cellulose derivatives, starch, natural substances such as sugars such as arabic gum, and polyvinylpyrrolidone, Includes synthetic polymeric materials such as water soluble polyvinyl compounds such as acrylamide polymers. Other synthetic polymeric materials include dispersed vinyl compounds in the form of latex.

Further, a binder of a vinyl addition polymer soluble in an organic solvent can also be used.

The support used for the light-sensitive material and the image-receiving material in the present invention can withstand processing pressure or processing temperature. Common supports include glass, paper,
Not only fine paper, coated paper, art paper, synthetic paper, metal and its analogues are used, but also acetyl cellulose film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film and related products. Includes film or resin material. Further, a paper support laminated with a polymer such as polyethylene can also be used. US Patent 363408
The polyester films described in Nos. 9 and 3725070 are preferably used.

The light-sensitive material of the present invention comprises a protective layer, an antistatic layer, and
Auxiliary layers such as an anti-curl layer, a peeling layer and a matting agent layer can be provided. Particularly, the protective layer preferably contains an organic or inorganic matting agent for the purpose of preventing adhesion.

In addition, anti-foggants, fluorescent whitening agents, anti-fading agents, anti-halation and anti-radiation dyes, pigments (including white pigments such as titanium oxide), and the color of the materials are adjusted as necessary for the light-sensitive materials and image-receiving materials. Alternatively, it may contain a coloring pigment, a thermal polymerization inhibitor, a surfactant, a dispersed vinyl compound or the like.

Various exposure means can be used in the present invention. Generally, commonly used light sources such as sunlight, strobes, flash lamps, tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser beams, and CRT light sources, plasma light sources, fluorescent tubes, light-emitting diodes, etc. are used as light sources. be able to. Also,
It is also possible to use an exposure means which is a combination of a micro shutter array using LCD (liquid crystal) or PLZT (lanthanum-doped lead titan zirconate) and a linear light source or a planar light source.

In the present invention, the layer containing the photosensitive microcapsules can be heated before and / or during and / or after exposure in order to enhance sensitivity.

In the present invention, the image is developed on the exposed element by a method of washing the unexposed, non-insolubilized areas with a solvent, by thermal transfer of the unexposed, non-hardened areas, or by other methods known to those skilled in the art. You can also In the case of washing with a solvent, an organic solvent can be used, but an alkaline aqueous solution can also be used as a developing solvent. Suitable developing solutions include alkali carbonates such as sodium carbonate solutions; alkali hydroxides such as sodium hydroxide solutions; mixtures thereof; lower alcohols such as ethanol, isopropanol and the like and aranolamines such as ethanolamine, propanolamine, 2- Aqueous solutions such as diethylaminoethanol; and the like.

The presence of a surfactant in the developing solution aids in clean development of the element. The alkaline strength of the developing solution depends on the particular composition used. Further, the developer may contain a dye, a pigment and the like. The developed image is then rinsed with distilled water,
It can also be dried and optionally post-baked.

"Example" Example 1 Using the photopolymerization initiator solutions A-1 to A-2 shown in Table 1, photopolymerizable compositions B-1 to B-2 shown below were prepared.

Pentaerythritol tetraacrylate 1.0 g Benzyl methacrylate / methacrylic acid (molar ratio 73/27 copolymer) 0.8 g Acetone 5 g Methyl ethyl ketone 10 g Propylene glycol monomethyl ether acetate 5 g Photopolymerization initiator solution (shown in Table 1) X g The resulting photopolymerizable compositions B-1 to B-2 were coated on a 100 μm polyethylene terephthalate film to a film thickness of 2 μm and dried at a temperature of 100 ° C. for 2 minutes, and further the following overcoat layer was formed to a film thickness of 1 μm. To 100 ° C. and dried for 2 minutes to obtain photosensitive sheets 1 and 2.

[Coating liquid for overcoat layer]

Water 98 g Polyvinyl alcohol 1.7 g Hydroxypropyl methylcellulose 1.7 g Polyvinylpyrrolidone 8.7 g For exposure, a step wedge (density step 0.15, density step number 0-15
Light was irradiated using a xenon lamp (manufactured by Ushio Co., Ltd.) through the Fuji Step Guide P (manufactured by Fuji Photo Film Co., Ltd.). After exposure, it was developed using a developer having the following formulation.

[Developer]

Anhydrous sodium carbonate 10 g Butyl cellosolve 5 g Water 1 After development, the step of the wedge with a small exposure was eluted and the polyethylene terephthalate surface appeared, so the maximum step number corresponding to the step wedge was determined as the step number of the photosensitive material.
The higher the number of steps, the higher the sensitivity.

The results are shown in Table 2.

As can be seen from Table 2, when the compound having an electron-withdrawing Cl group in the indolenine nucleus of the present invention is used, a remarkable photosensitivity improving effect is obtained as compared with the case where a compound having no Cl group is used. Bring

In the photosensitive sheet 1 of the comparative example, since the photosensitive layer was not cured, the image flowed and the number of steps could not be specified.

Example 2 Photopolymerization initiator solution C-1 to C-2 shown in Table 3 consisting of organic cationic dye / image boron anion salt and other additives
To the solution, 3.3 g of polyisocyanate [SUMIDYULE N-75 (Sumitomo Chemical Co., Ltd.)] was added, and this solution was used as a color former.
A solution of 12 g of Perscript Red I-6-B (manufactured by Ciba Geigy) in 50 g of trimethylolpropane triacrylate is mixed. This mixed solution was added to 154 g of water with polystyrene soda sulfonate (National Starch Versa
TL50 ² ) 4.3 g was dissolved, and then pectin 5.1 g was further dissolved therein, and the mixture was added to an aqueous solution whose pH was adjusted to 6.0 and emulsified and dispersed. To this dispersion was added 44 g of water, 3.9 g of melamine and 6.5 g of 37% formalin in advance at 60 ° C. for 30 minutes, and the mixture was mixed and the pH was adjusted to 6.0. Then, the temperature was raised to 65 ° C., and the reaction was carried out for 3 hours with stirring. To this reaction solution, 7.7 g of urea was added, then the pH was adjusted to 9.5 with NaOH solution, and the particle size was 3.5 μm.
Microcapsule liquids D-1 to D-2 were obtained.

[Preparation of Photosensitive Sheet and Image-Receiving Sheet] Capsule liquids D-1 to D-2, 5 g respectively, thus obtained
15% polyvinyl alcohol aqueous solution 1.53 g, distilled water 3.47 g,
0.57 g of starch was added to prepare a coating solution. This was coated on art paper using Cotain Globe 10 and dried at 50 ° C. for 15 minutes to obtain photosensitive sheets 3 to 4.

On the other hand, 0.6g of 48% SBR lattex, 4g of 10% etherified starch aqueous solution, 2.1g of zinc carbonate and 50g of sodium silicate in 21.8g of water.
% Aqueous solution 1.3 g, sodium hexametaphosphate 0.1 g, and acid clay clay 13 g were added, and the mixture was stirred with a homogenizer for 15 minutes.

This was coated on art paper using Cotain Globe 18 and dried at 100 ° C. for 2 minutes to obtain an image receiving sheet.

[Image playback and results]

The image was reproduced as follows. Xenon lamp (USHIO Co., Ltd.)
Manufactured by Fuji Photo Film Co., Ltd. (Fuji Step Guide P)
Light was shined through. After exposure, stack the exposed photosensitive sheet and the image-receiving sheet so that the coated surfaces face each other, and
It was passed through a pressure roller of 100 kg / cm. The capsules in the unexposed area were destroyed and transferred to the image receiving sheet. The transferred part gave a clear image with a density of 1.0. The density of the portion corresponding to the exposed area changes depending on the exposure amount, but the sensitivity was set to have a minimum number of exposure steps at which the density was 0.1 or less (corresponding to foot sensitivity).
That is, the larger the number of exposure steps, the higher the sensitivity. The results are shown in Table 4.

As can be seen from Table 4, the use of the compound having an electron-withdrawing Cl group in the indolenine nucleus of the present invention shows higher sensitivity than the use of the compound having no Cl group.

Example 3 Instead of the photopolymerization initiator (b) of Example 1 Samples were prepared in the same manner as in Example 1 except that each was used. When these samples were tested in the same manner as in Example 1, all had higher sensitivity than Comparative Example 1 and showed sensitivity almost equal to that when the photopolymerization initiator (b) was used.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-64-60606 (JP, A)

Claims (2)

[Claims] 1. A polymerizable compound having an ethylenically unsaturated bond, and an organic boron compound anion salt of an organic cationic dye compound represented by the following general formula (I), wherein the organic cationic dye compound is A photopolymerizable composition represented by the following general formula (II). General formula (I) Where D ⁺ is a cationic dye of the general formula (II); R ¹ ,
R ² , R ³ and R ⁴ may be the same or different, and an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group,
Aralkyl group, substituted aralkyl group, alkaryl group, substituted alkaryl group, alkenyl group, substituted alkenyl group,
A group selected from an alkynyl group, a substituted alkynyl group, an alicyclic group, a heterocyclic group and a substituted heterocyclic group;
R ¹ , R ² , R ³ and R ⁴ may be a cyclic structure in which two or more groups are bonded. General formula (II) Here, R ¹¹ and R ¹² each represent an alkyl group,
L ¹ , L ² and L ³ represent a methine group. n represents an integer of 0 to 4, and A ¹ , A ² , A ³ , A ⁴ , B ¹ , B ² , B ³ and B ⁴ are each a hydrogen atom or an electron-withdrawing group (hamet σ> 0).
Represents However, at least ^one of A ¹ , A ² , A ³ , A ⁴ , B ¹ , B ² , B ³ , and B ⁴ represents an electron absorbing group. 2. The photopolymerizable composition according to claim 1, wherein the polymerizable compound having an ethylenically unsaturated bond is encapsulated in microcapsules.